CN106459352A - Retroreflective articles with wash durable bead bond layers - Google Patents

Retroreflective articles with wash durable bead bond layers Download PDF

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Publication number
CN106459352A
CN106459352A CN201580032629.7A CN201580032629A CN106459352A CN 106459352 A CN106459352 A CN 106459352A CN 201580032629 A CN201580032629 A CN 201580032629A CN 106459352 A CN106459352 A CN 106459352A
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CN
China
Prior art keywords
layer
tack coat
reactant mixture
retroreflective articles
polyurethane
Prior art date
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Granted
Application number
CN201580032629.7A
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Chinese (zh)
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CN106459352B (en
Inventor
布鲁斯·H·爱德华兹
什里·尼瓦斯
夏颖
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3M Innovative Properties Co
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3M Innovative Properties Co
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Publication of CN106459352A publication Critical patent/CN106459352A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/58—No clear coat specified
    • B05D7/582—No clear coat specified all layers being cured or baked together
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3221—Polyhydroxy compounds hydroxylated esters of carboxylic acids other than higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C08K5/5465—Silicon-containing compounds containing nitrogen containing at least one C=N bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/12—Reflex reflectors
    • G02B5/126—Reflex reflectors including curved refracting surface
    • G02B5/128—Reflex reflectors including curved refracting surface transparent spheres being embedded in matrix
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B7/00—Mountings, adjusting means, or light-tight connections, for optical elements
    • G02B7/002—Mounting on the human body

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Retroreflective articles include a layer of optical elements, and a polyurethane bead bond layer. The optical elements include transparent microspheres, and at least one reflective layer. The polyurethane bead bond layer is the reaction product of a reaction mixture of at least one aliphatic polycarbonate polyol and at least one polyisocyanate, and the reaction mixture is free of polyols containing unsaturated groups. The retroreflective articles have improved wash durability.

Description

Retroreflective articles with washability pearl tack coat
Technical field
It relates to retroreflective articles and making and method using these retroreflective articles, specifically, it is related to have The retroreflective articles of washability.
Background technology
Have been directed towards being widely applied and develop multiple products for combining retroreflective phenomenon.Retroreflective articles have makes big portion The ability for dividing incident illumination to return light source.This unique ability promotes the extensive application of retroreflective security product.Except traffic and warning Outside label etc., retroreflective articles are incorporated therein by multiple medicated clothings and similar articles knapsack etc..Hand in motor vehicles Logical work nearby or the crowd for taking exercise are needed for being evident that, so that they are not clashed into through motor vehicles by institute. When retroreflective articles are worn, retroreflective by retroeflection from motor vehicle headlamp light highlighting the presence of people.
Retroreflective articles generally have optical lens components layer, polymeric beads tack coat, reflecting layer, and also can be with substrate Layer.Optical lens components are usually the microsphere being partially embedded in polymeric beads tack coat.Reflecting layer is usually aluminum, silver or is situated between Matter mirror, which is generally arranged on the embedded part of microsphere.The light for being irradiated to retroreflective articles front surface passes through microsphere and warp Reflecting layer is reflected to reenter microsphere, and herein, the direction of light is subsequently changed with return light source of advancing.Therefore, example Such as, when vehicle head lamp is irradiated to retroreflective articles, some are reflected back toward the driver of vehicle from the light of headlamp.
In general, it is not necessary to or even undesirable product of entirely wearing all has retroreflective, is therefore often pasted using retroeflection Flower.These retroeflection appliques can subsequently be attached to clothes product or other products to prepare retroreflective articles.In some cases, pass through Following manner prepares retroeflection applique：Microsphere layer is partially embedded in thermoplastic carrier's web, divides it in microsphere protuberance Upper applying reflecting material, subsequently forms pearl tack coat on coated microsphere.Generally apply on the back surface of pearl tack coat Pressurization sensitive adhesive, and stripping backing member is placed on binding agent, until applique is fixed to substrate.By the applique for being completed (otherwise referred to as transfer sheet) is supplied to clothing assembler in this form, and clothing assembler is by removing stripping backing member And applique is fixed to clothes product by the outer surface that applique is adhered to clothes product.Carrier is subsequently separated with applique to expose Microsphere, so that applique can retroreflection light.
Multiple retroreflective articles are prepared and have described.Wherein, the retroreflective articles for having prepared be with pearl tack coat Retroreflective articles, the pearl tack coat include polyurethane material.In Japanese Patent Publication No.JP 8-158268, one kind is described The method of manufacture optical reflection coating medicated clothing, in the method, forms resin bed on fiber medicated clothing, and wherein resin bed has conduct Its main body and the polyurethane resin comprising lemel such as aluminum, and formed comprising ball on the resin bed with dry-coated method The single resin bed or compound tree lipid layer of the acrylate of shape clear glass pearl or polyurethane resin.United States Patent (USP) No.5, 976,669 (Fleming) describe the retroreflective articles with the retro-reflection element being embedded in adhesive layer, and the adhesive layer is comprising solid Body polyurethane.The polyurethane includes soft chain segment, hard segment, oxyalkylene segment and urethane moiety.PCT Publication WO 2009/011989 Teach a kind of for preparing the method that can vulcanize retroeflection sheet material, wherein the method includes：Reactant mixture is provided, the reaction is mixed Compound is unsaturated many comprising at least one diisocyanate, at least one polyisocyanates, at least one polyhydric alcohol, at least one First alcohol and at least one chain extender；The reactant mixture is coated with the carrier web for including retro-reflection element；Make the reaction mixing Thing solidifies；And remove carrier.
Content of the invention
Disclosed herein is retroreflective articles and the method for making and using these retroreflective articles.In some embodiments, Retroreflective articles include the layer of polyurethane pearl tack coat and the optical element being partially embedded in pearl tack coat.Optical element includes Bright microsphere and at least one reflecting layer.Product of the polyurethane pearl tack coat comprising following reactant mixture, the reaction is mixed Compound is comprising at least one aliphatic polycarbonate polybasic alcohol and at least one polyisocyanates, and the reactant mixture is not contained Polyhydric alcohol containing unsaturated group.The reactant mixture can include other additive, such as other polyhydric alcohol, silane coupled Agent and curing catalysts.The retroreflective articles are washabilityes.
The invention also discloses clothes product.In some embodiments, clothes product include with the first first type surface and The fabric of the second first type surface；And the retroeflection applique with the first first type surface attachment of the fabric.Retroeflection applique includes polyurethane pearl Tack coat, the layer of the optical element being partially embedded in pearl tack coat and the supporting layer with the attachment of polyurethane pearl tack coat.Optics Element includes Transparent microspheres and at least one reflecting layer.Polyurethane pearl tack coat is many comprising at least one fatty poly-ester carbonate First alcohol and the product of at least one polyisocyanates, and the reactant mixture does not contain the polyhydric alcohol containing unsaturated group. Supporting layer includes adhesive phase, film layer, tissue layer or non-woven layer, and supporting layer is attached with the first first type surface of fabric.
Invention also describes the method for preparing product.In some embodiments, the method for preparing product includes：There is provided Polymer carrier layer with the first first type surface and the second first type surface；Transparent microspheres are provided；Transparent microspheres are partly embedding Enter in the first first type surface of polymer carrier layer so that the pearl is dashed forward from the first first type surface of polymer carrier layer at least in part Go out, to form microsphere layer；One is deposited at least a portion of the first first type surface of polymer carrier layer and microsphere layer Or multiple reflecting layer；There is provided the reaction comprising at least one aliphatic polycarbonate polybasic alcohol and at least one polyisocyanates to mix Compound, wherein reactant mixture do not contain the polyhydric alcohol containing unsaturated group；Reactant mixture is applied to microsphere layer；And make Reaction mixture cured is to form polyurethane pearl tack coat.The method may also include and for supporting layer be attached to polyurethane pearl bonding Layer.Removing polymer carrier layer generates washability retroreflective articles.
Description of the drawings
With reference to the detailed description below in conjunction with accompanying drawing to the various embodiments of the disclosure, this Shen can be more fully understood Please.
Fig. 1 shows the sectional view of the embodiment of the intermediate of the disclosure.
Fig. 2 shows the sectional view of the embodiment of the intermediate of the disclosure.
Fig. 3 shows the sectional view of the embodiment of the product of the disclosure.
Fig. 4 shows the sectional view of the embodiment of the product of the disclosure.
Fig. 5 shows the top view of the embodiment of the product of the disclosure.
In the following description of shown embodiment, accompanying drawing is have references to, and by way of illustration in these accompanying drawings In be shown in which to implement the various embodiments of the disclosure.It should be appreciated that in the situation without departing from the scope of the present disclosure Under, it is possible to use embodiment and the change in structure can be carried out.These accompanying drawings are not necessarily drawn to scale.Used in accompanying drawing Similar label indicate similar part.It will be appreciated, however, that using not for the label for being finger in given accompanying drawing It is intended to the restriction in another accompanying drawing with the part of identical labelled notation.
Specific embodiment
So that various products is had retroreflective demand and result in and be increasingly using retroreflective articles.In some applications, Have can whole product retroreflective；One of product in other application, can be made by using one or more retroeflection appliques Divide with retroreflective.Retroreflective articles generally have optical element layer, polymeric beads tack coat and reflecting layer.Optical element is usually The microsphere being partially embedded in polymeric beads tack coat.Reflecting layer is usually aluminum, silver or dielectric mirror, and which is generally arranged at microsphere On the embedded part of body.The light of retroreflective articles front surface is irradiated to through microsphere and the reflection of reflected layer is micro- to reenter Spheroid, herein, the direction of light is subsequently changed with return light source of advancing.Thus, for example, when vehicle head lamp is irradiated to back When penetrating product, some are reflected back toward the driver of vehicle from the light of headlamp.This causes when people wears retroreflective articles, vehicle When driver notices that the his or her time does not far wear retroreflective articles early than this person, driver will be noted that the his or her time. These retroreflective articles and applique can be attached to the product of broad range, including from bicycle and motor vehicles to the clothing of broad range Each of thing jacket, vest, shirt, shoes, medicated cap etc..
In the disclosure, product is described, these products have polyurethane pearl tack coat, the polyurethane pearl tack coat strengthens The washability of the ruggedness of retroreflective articles, particularly retroreflective articles.Polyurethane pearl tack coat is by comprising polycarbonate polyol Prepared by reactant mixture.Due to desirably obtained with retroreflective product for washable, so washability particular importance. So-called washability, which means that product can be washed the number of times without losing its retro-reflective properties.
Washability is especially desirable feature for pending retroreflective articles.Therefore, very big effort has been made To provide this feature.Wherein, the technology for having adopted includes：(contrary with the bead surface comprising reflecting layer on pearl layer Pearl layer surface on) place protective layer, between pearl and reflecting layer place protective layer, and change pearl tack coat so which has more Washability.Each of these schemes are respectively provided with merits and demerits.Protective layer is put on pearl layer or pearl and reflecting layer it Between the meaning be：When light enters product and leaves after retroeflection, the protective layer is in the light path that light is passed through.Although Sizable progress is achieved in terms of minimizing the harmful effect to the retroreflection characteristics of the product comprising these protective layers, but light In road, the presence of these floor can be had undesirable effect to the performance of these products.In addition, be coated with these protective layers on product needing Other procedure of processing is wanted, and therefore increased cost, time and the manpower for preparing these products.
Pearl tack coat is modified so that its have more washability and thus improve retroreflective articles washability in terms of Also sizable effort is made that.Some during these are attempted include polyurethane material used in pearl tack coat.For example, the U.S. Patent No.5,976,669 (Fleming) describe the retroreflective articles with the retro-reflection element being embedded in adhesive layer, the bonding Oxidant layer includes solid polyurethane.The polyurethane includes soft chain segment, hard segment, oxyalkylene segment and urethane moiety.Solid used Polyurethane material is based on isocyanate-terminated polyurethane prepolymer, and the prepolymer is by providing soft chain segment and for polyester-poly- alkane Prepared by the carbocyclic ring polyisocyanates of the polyhydric alcohol of epoxide-polyester ABA block polymer and offer hard segment.
In the disclosure, the polyurethane pearl tack coat for being prepared by polycarbonate polyol is described.The polyurethane of the disclosure Pearl tack coat has the washability for improving compared to the polyurethane pearl tack coat for being prepared by PEPA.The disclosure some In embodiment, some polyester groups are may be present in polyhydric alcohol synthon, but mainly Merlon linking group is present In polyhydric alcohol synthon.
Except as otherwise noted, otherwise used in specification and claims expression characteristic size, quantity and physics spy All numerals of property are construed as all being modified by term " about " in all cases.Therefore, unless indicated to the contrary, otherwise The numerical parameter that lists in description above and appended claims is approximation, and these approximations can be according to this area Technical staff using teachings disclosed herein seek obtain desired characteristic and change.The numerical value that is stated with end value Scope includes the whole numerals (as 1 to 5 includes 1,1.5,2,2.75,3,3.80,4 and 5) for being included in the range of this and the scope Interior any scope.
Except non-content is clearly specified, singulative " one " otherwise used in this specification and claims, " Kind " and " described " cover the embodiment with multiple referents.For example, " one layer " cover with one layer, two-layer or The embodiment of more layers.Unless the context clearly dictates otherwise, otherwise as used in this explanation and claims, art Language "or" is typically to include the meaning use of "and/or".
As used herein, term " binding agent " refers to that the polymer-type that can be used to two adherends adhere to each other is combined Thing.The example of binding agent is contact adhesive, heat-activatable adhesive and laminating adhesive.
Those skilled in the art know, and contact adhesive composition has including the spy including following characteristic Property：(1) adhesion strength strong and lasting at room temperature；(2) can adhesion with the pressure less than finger pressure；(3) have solid enough Determine to the ability on adherend；And (4) enough cohesive strength is to make which be cleanly removed from adherend.Have been found that very well To play the material of contact adhesive effect be polymer, the polymer is designed and formulated to exhibit required viscoelasticity, from And cause the expectation balance of viscosity, peel adhesion and shearing retentivity.The not simple process of the appropriate balance of acquisition property.
Heat-activatable adhesive is not tacky at room temperature, but becomes tacky at elevated temperatures and can be bonded to substrate. These binding agents generally have Tg or the fusing point (Tm) higher than room temperature.When temperature increases to over Tg or Tm, storage moduluss are usual Can reduce and binding agent becomes tacky.
Laminating adhesive (otherwise referred to as contact adhesive) is for being designed to be formed immediately after the distribution and two bases The binding agent of the bonding at bottom.Once being assigned with binding agent, just have the restriction time, sometimes referred to as wherein binding agent can be formed with " open hour " of the bonding of two substrates.Once the open hour are over, laminating adhesive is just no longer able to form bonding Agent bonds.The example of laminating adhesive is hot-melt adhesive, polymeric material or curable poly- to be formed in liquid medium The solution of the material of compound material or dispersion and curable adhesive.Laminating adhesive is applied in substrate, makes second Substrate is contacted with adhesive surface, and the three-layer structure for being formed is cooled down, is dry and/or be cured to form laminates.Layer The example for closing binding agent includes that (glue stick is to form the heat fusing type bonding of bonding in cooling to glue stick used in hot glue gun Agent)；Casein glue, sometimes referred to as " white glue " (casein glue is the aqueous dispersion for forming bonding when drying)；And cyano group third Olefin(e) acid ester adhesive (the binding agent solidification to form bonding when air is exposed to).
Except as otherwise noted, otherwise term " transparent " and " optically transparent " used interchangeably and refer to product, film or Binding agent is with high transmission rate at least a portion of visible spectrum (about 400 to about 700nm).So-called in visible spectrum extremely High transmission rate in a few part, which means at least 50% light transmittance, in some embodiments at least 70% light transmittance Or even greater than 90% light transmittance.
As used herein, term " polymer " " refers to the polymeric material for homopolymer or copolymer.As used herein, art Language " homopolymer " refers to as a kind of polymeric material of the product of monomer.As used herein, term " copolymer " refer to be at least The polymeric material of the product of two kinds of different monomers.
Term " polyurethane " is used for description comprising the organic group for being connected by urethane (sometimes referred to as carbamate) key The polymer of group's chain.Urethane bond has structure-NH- (CO)-O-, and wherein (CO) refers to carbonyl group C=O.Polyurethane is by polyisocyanate Cyanate is prepared with the reaction of polyhydric alcohol.Term " polyisocyanates " refers to having comprising at least two isocyanate groups Machine material.Isocyanate groups have structure-N=C=O, and polyisocyanates has formula Ra(N=C=O)n, its Middle n is equal to the number of two or more, and RaIt is n valency organic group, the organic group can be aliphatic group, aromatic group Or combinations thereof, and can be polymer-based group.When n is 2, the material is diisocyanate, and when n is 3, the material is Triisocyanate, when n is 4, the material is tetraisocyanate etc..Term " polyol " is referred to comprising at least two oh groups Organic material.Oh group has structure-OH, and polyhydric alcohol has formula Rb(OH)n, wherein n is equal to 2 or more Big number, and RbIt is n valency organic group, the organic group can be aliphatic group, aromatic group or combinations thereof, and And it is typically the polymerized unit comprising functional group's key.When n is 2, the material is dihydroxylic alcohols, and when n is 3, the material is ternary Alcohol, when n is 4, the material is tetrahydroxylic alcohol etc..Functional group's key is frequently utilized for describing polyhydric alcohol.For example, " polyether polyol " is referred to Wherein RbPolyhydric alcohol of the group comprising ehter bond, " PEPA " refers to wherein RbPolyhydric alcohol of the group comprising ester bond, " poly- carbonic acid Ester polyol " refers to wherein RbPolyhydric alcohol of the group comprising carbonic acid ester bond.Ehter bond has formula-O-.Ester bond has formula Structure-O- (CO)-, wherein (CO) refers to carbonyl group C=O.Carbonic acid ester bond has formula-O- (CO)-O-, wherein (CO) Refer to carbonyl group C=O.Aliphatic polyol is the aliphatic polyol for only including aliphatic hydrocarbon group, that is to say, that should Aliphatic polyol does not include aromatic hydrocarbon radical.Unsaturated polyol be comprising the polynary of one or more unsaturated groups Alcohol, that is to say, that the unsaturated polyol includes with formula-RC=CH2End group, wherein R be hydrogen or alkyl group.
Term " alkyl " refers to the univalent perssad for alkyl, and which is saturated hydrocarbons.Alkyl can be straight chain, side chain, Ring-type or combinations thereof, and generally have 1 to 20 carbon atom.In some embodiments, alkyl includes 1 to 18,1 To the carbon atom of 12,1 to 10,1 to 8,1 to 6 or 1 to 4.The example of alkyl group include but is not limited to methyl, ethyl, positive third Base, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, just base, cyclohexyl, n-heptyl, n-octyl, 3- methyl amyl, And ethylhexyl.
Term " aryl " refers to the univalent perssad for aromatics and carbocyclic ring.Aryl can be connected with aromatic ring with 1 to 5 or thick The ring of conjunction.Other ring structures can be aromatics, non-aromatic or combinations thereof.The example of aromatic yl group includes but is not limited to benzene Base, xenyl, terphenyl, anthryl, naphthyl, acenaphthenyl, anthraquinonyl, phenanthryl, anthryl, pyrenyl, base and fluorenyl.
Term " alkylidene " refers to the divalent group for alkyl.Alkylidene can be straight chain, side chain, ring-type or it Combination.Alkylidene generally has 1 to 20 carbon atom.In some embodiments, alkylidene includes 1 to 18,1 to 12,1 To the carbon atom of 10,1 to 8,1 to 6 or 1 to 4.The radical center of alkylidene can be in identical carbon atoms (i.e. alkylidene radical) or different carbon On atom.Alkylidene group can also be replaced by one or more alkyl groups or aromatic yl group.
Term " arlydene " refers to the divalent group for carbocyclic ring and aromatics.The group have connected, condense or they Combination one to five ring.Other rings can be aromatics, non-aromatic or combinations thereof.In some embodiments, sub- Aryl has at most 5 rings, at most 4 rings, at most 3 rings, at most 2 rings, or 1 aromatic ring.For example, arylene group can be Phenylene.Arylene group can also be replaced by one or more alkyl groups or aromatic yl group.
Term " alkoxyl " refers to the univalent perssad with formula OR structure, and wherein R is alkyl group.
Term " acrylic compounds " is referred to formula H2C=CR1-C(O)-OR2Compound, wherein (CO) refer to carbonyl Base group C=O, R1It is hydrogen or-CH3, and R2It is hydrogen, alkyl or hydroxyalkyl.
As used herein, term " thermoplasticity ", " non-thermal plasticity " and " thermosetting " refers to the property of material.Thermoplastic It is to melt when heat is applied and/or flow, the resolidification in cooling, the material for melting again and/or flowing when heat is applied.Heat Plastic material only experiences physical change in heating and cooling, without there is measurable chemical change.Non-thermoplastic material It is immobilising material during the heat for being in application to the temperature that many materials start degraded.Thermosets are curable materials, its There is irreversible solidification in heating or solidification, such as become crosslinking.Once solidification, thermosets would not when heat is applied Measurably melt or flow.
Disclosed herein is the method for preparing retroreflective articles.These methods include：There is provided and there is the first first type surface and the second master The polymer carrier layer on surface；Transparent microspheres are provided；Transparent microspheres are partially embedded into the first master of polymer carrier layer In surface so that the pearl is projected from the first first type surface of polymer carrier layer at least in part, to form microsphere layer；Poly- One or more reflecting layer are deposited at least a portion of first first type surface of compound carrier layer and microsphere layer；And bag is provided Reactant mixture containing at least one aliphatic polycarbonate polybasic alcohol and at least one polyisocyanates；Reactant mixture is applied Add to microsphere layer；And reaction mixture cured is made to form polyurethane pearl tack coat.Reactant mixture can comprising a kind of with On polyhydric alcohol, but the polyhydric alcohol being free from containing unsaturated group.The product being consequently formed is intermediate and can pass through to move It is changed into retroreflective articles except polymer carrier layer.
In some embodiments, sink at least a portion of the first first type surface of polymer carrier layer and microsphere layer The one or more reflecting layer of product include：Reflective metals are deposited to the selected portion of microsphere layer.The selective deposition can be led to Cross and be embodied in various ways, for example, some parts on the surface can be covered to prevent metal deposit.In other embodiments, exist One or more reflecting layer being deposited at least a portion of first first type surface of polymer carrier layer includes：By one or more layers electricity Dielectric material is deposited on the selected portion of microsphere layer.In general, multi-layer dielectric material is deposited to form electrolyte Reflecting layer, the reflecting layer is sometimes referred to as dielectric mirror.The combination of these sedimentation types can also be used.
Multiple material is applied to said method.Described below is the example of these materials.
The combination of multiple material and material is applied to polymer carrier layer.In many embodiments, polymer carrier layer For thermoplastic polymer carrier's layer, but in other embodiments, polymer carrier layer may include elastomer polymer carrier Layer, in some embodiments, polymer carrier layer can even is that contact adhesive or heat-activatable adhesive.Polymer support Layer generally includes thermoplastic polymer carrier's layer.In some embodiments, thermoplastic polymer carrier's layer can be independent stratum；? In other embodiments, thermoplastic polymer carrier's layer can include thermoplastic polymer carrier's material on the first first type surface of sheet material Material coating.Sheet material may include such as paper wood, polymeric film etc..The example of available polymer carrier materials include polrvinyl chloride, Polysulfones, polyolefin polyethylene, polypropylene and polybutene, polyester etc..
The layer of Transparent microspheres is embedded in forming part on the surface of polymer carrier layer.By Transparent microspheres are rushed down The monolayer for falling in polymer carrier layer to assemble Transparent microspheres, this is fixed on microsphere in required provisional distribution.Poly- Compound carrier layer generally receives thermal softening.The usual dense accumulation as far as possible of microsphere, ideally with its most tight hexagonal arrangement side Formula, to realize very good retroeflection brightness, and can be arranged so as to by any conventional applying technique, such as printing, screen cloth, Rush down or hot rolling.After cooling, polymer carrier layer makes microsphere keep in required arrangement.
Generally, Transparent microspheres be shaped as made of substantially spherical to provide most all uniform effective retroeflection.Microsphere is base Transparent in sheet, at utmost to reduce light absorbs so that the incident illumination of larger percentage is able to retroeflection.The usual base of microsphere Colourless in sheet, but it is also possible to which that some other modes are painted or coloured.
Microsphere can be made by glass, non-vitreous ceramic compositionss or synthetic resin.Glass and ceramic microspheres are Particularly suitable, because their microspheres often than being made up of synthetic resin are harder and more robust.The showing of available microsphere Example following United States Patent (USP) 1,175,224,2,461,011,2,726,161,2,842,446,2,853,393,2,870,030, 2,939,797、2,965,921、2,992,122、3,468,681、3,946,130、4,192,576、4,367,919、4,564, 556th, it is described in 4,758,469,4,772,511 and 4,931,414.
Microsphere generally has the average diameter at about 30 microns to 200 micrometer ranges.Microsphere less than the scope Lower level retroeflection is often provided, and more than the scope microsphere can for applique give undesirable rough grain or It is flexible that person can undesirably reduce which.Microsphere generally has the refractive index of about 1.7 to about 2.0, and the scope is typically considered to can For in exposed lens retroreflecting product.
As it appears from the above, reflecting layer is applied at least a portion of microsphere layer.Reflecting layer can be reflective metal layer, electricity Dielectric reflective layer or combinations thereof.
Reflective metal layer is the mirror plate reflective metal to form reflective metal layer coating.The technology is conducive to retro-reflection element (optical element and reflecting material) is arranged to substantially consistent retroeflection direction.Retro-reflection element (is coated with the micro- of reflecting material The surface portion of spheroid) size can partially by apply reflecting material before by microsphere be embedded in polymer in depth Degree is controlled to be controlled.
Reflecting material can be the layer for including to be capable of the metal element of reflected light in a mirror fashion.Various metals can be used for carrying For specular reflective metal layers.Aluminum that these include element form, silver, chromium, gold, nickel, magnesium etc., and combinations thereof.From performance For angle, aluminum and silver are particularly suited for use in the metal in reflecting layer.Metal can be for being such as coated with by vacuum deposition method, steam It is continuous coated that method, chemical deposition or electroless plating method are produced.It should be appreciated that for aluminum, some metals can assume metal oxygen Compound and/or the form of metal hydroxidess.Aluminum metal and silver metal for needed for because they often provide highest retroeflection Brightness.Metal level should be sufficiently thick to reflect incident illumination.Generally, reflective metal layer is for about 50 nanometers to 150 nanometer thickness.
Electrolyte reflecting layer is dielectric mirror.Dielectric mirror can be similar to 3,700,305 He of United States Patent (USP) for authorizing Bingham Known media mirror disclosed in 4,763,985.Dielectric mirror is usually multi-ply construction, and wherein certain layer of refractive index is n2And arrange The refractive index of transparent material layer thereon is n1, (refractive index is n to transparent material reverse side1) with refractive index be n3Material, Wherein n2And n3Both refractive indexs are at least 0.1, more typically at least 0.3, more than or less than n1.Transparent material is logical Often have with odd-multiple (that is, 1,3,5,7...) about 1/4 wavelength light (about 380 to about 1000 nanometers of wave-length coverage) corresponding The layer of optical thickness.Therefore, n2>n1<n3Or n2<n1>n3, and being all higher than per the refractive index of material in one side of clear layer Or respectively less than n1.Work as n1More than n2And n3Both when, n1In the range of 1.7 to 4.9, n2And n3In the range of 1.2 to 1.7. On the contrary, working as n1Less than n2And n3Both when, n1In the range of 1.2 to 1.7, and n2And n3In the range of 1.7 to 4.9. Dielectric mirror generally comprises adjacent material array, and wherein at least one material is the form of layer, and with alternate refractive index sequence Row.Adjacent array is generally adjacent with lens element with two to seven layers, more typically has three to five layers with lens element phase Adjacent.Dielectric mirror can provide extraordinary retroreflective, although its be generally not heel-tap reflex metal level equally effective reflecting element.
Wherein, the chemical compound lot that can be used for providing the transparent material in required ranges of indices of refraction is：High index of refraction material Material, such as CdS, CeO2、CsI、GaAs、Ge、InAs、InP、InSb、ZrO2、Bi2O3、ZnSe、ZnS、WO3、PbS、PbSe、 PbTe、RbI、Si、Ta2O5、ZrO2、Te、TiO2；Low-index material, such as cryolite, Al2O3、AlF3、CaF2、CeF3、LiF、 MgF2、Na3AlF6、ThOF2, perfluoropropene and vinylidene fluoride elastomer copolymer (refractive index>>1.38) etc..Other materials In Thin Film Phenomena, K.L.Chopra, page 750, McGraw-Hill Book Company, N.Y., (1969) (K.L.Chopra,《Film phenomenon》, page 750, the McGraw-Hill Book Co in New York, 1969) in Description.Layer of the specially suitable dielectric mirror comprising following material：SiO2、CaF2、MgF2、ZnS、Nb2O5、Ta2O5、ZrO2Or they Combination.In some embodiments, electrolyte reflecting layer includes CaF2, ZnS or combinations thereof layer.
Disclosed method also includes：There is provided comprising at least one aliphatic polycarbonate polybasic alcohol and at least one polyisocyanate The reactant mixture of cyanate；Reactant mixture is applied to microsphere layer；And reaction mixture cured is made to form poly- ammonia Ester pearl tack coat.Aliphatic polycarbonate polybasic alcohol does not include unsaturated group, and can be dihydroxylic alcohols or higher functionality Polyhydric alcohol.Reactant mixture can additionally comprise other components, and such as other polyhydric alcohol is (as long as these other polyhydric alcohol are not Unsaturated polyol), silane coupler and curing catalysts.It may be desirable that reactant mixture includes stoichiometric(al) mistake Surplus polyisocyanates.So-called stoichiometric excess, which means the reactive isocyanate group being present in reactant mixture Number more than reactive hydroxyl groups number.
Multiple polyisocyanates are suitable to prepare polyurethane pearl tack coat.The example of suitably polyisocyanates includes any conjunction Suitable organic multiple isocyanate, aliphatic, alicyclic, araliphatic or aromatics, which may be used alone or in combination makes With.Although aromatics or aliphatic isocyanates be suitable, but in some embodiments, aromatic polyisocyanate is probably Specially suitable.Diisocyanate is an especially desirable class polyisocyanates.Can add comprising two or more isocyanide in molecule The low-level isocyanates of acid esters group and do not make the characteristic of resulting polymers that measurable change occurs.Suitable organic polyisocyanate Cyanate includes dicyclohexyl methyl hydride 4,4'- diisocyanate (so-called H12MDI), 1,3- bis- (isocyanatomethyl) ring Hexane, 1,3- bis- (1- isocyanate group -1- Methylethyl) benzene (so-called TMXDI), 3,5,5- trimethyl -1- isocyanate group - 3- isocyanato methylcyclohexane (so-called isophorone diisocyanate or IPDI), metaphenylene diisocyanate, right Phenylene vulcabond, 2,4 toluene diisocyanate, 2,6- toluene di-isocyanate(TDI), 4,4'- diisocyanate diphenyl Methane (so-called MDI), benzidine diisocyanate, naphthalene -1,5- diisocyanate, hexamethylene diisocyanate are (generally Referred to as HDI) and other alkylidene diisocyanate resins (for example, tetramethylene diisocyanate, decamethylene diisocyanate and Ten dimethylene diisocyanates), 4,4', 4 "-triphenylmethane triisocyanate, by comprising at most about 4 aromatic rings The polyphenyl methylene polyisocyanates of the phosgenation reaction generation of aniline/formaldehyde condensation product, two Carbimide. of dianisidine Ester, xylene diisocyanate, two (2- isocyanatoethyl) fumarate, two (2- isocyanatoethyl) hexamethylene- 4- alkene -1,2- dicarboxylic ester, two (2- isocyanatoethyl) carbonic esters and many other organic many isocyanides known in the art Acid esters.
Multiple polycarbonate polyols are suitable, including the alkylene oxide adduct of polycarbonate polyol.Term " epoxy Alkane " includes, for example, oxirane, 1,2 epoxy prapane, 1,2- epoxy butane, 2,3- epoxy butane, methyloxetane, ring Oxygen chloropropane etc. and their mixture.Polyhydric alcohol can be the polyhydric alcohol of dihydroxylic alcohols, trihydroxylic alcohol or higher functionality, typically For generally dihydroxylic alcohols be suitable.Specially suitable polycarbonate polyol is these dihydroxylic alcohols for being described by following formula 1：
HO-[(CH2)2CHR1(CH2)n-O-(CO)-O-]m-[(CH2)2CHR1(CH2)n]-OH
Formula 1
Wherein (CO) defines carbonyl group C=O, R1It is hydrogen or methyl；N is integer 2 or 3 so that work as R1For n during hydrogen it is 3, and work as R1It is 2 for n during methyl；And m is greater than 3 number, usual m is the number in the range of 3 23.
The molecular weight of polyol component is to determine a key factor of polymer final response.In general, molecular weight Higher, resulting polymers are more soft.Terms used herein " molecular weight " is number average molecular (Mn).Molecular weight as little as 500 Gram/mol and up to 10,000 gram/mol of polyhydric alcohol is suitable, or molecular weight ranges are at 500 grams/mol to 6, 000 gram/mol of polyhydric alcohol is suitable, and wherein molecular weight ranges are at 500 grams/mol to 3, and 000 gram/mol of polyhydric alcohol is Specially suitable, and most easily by commercially available.
Commercially available polycarbonate polyol is included with KURARAY POLYOL C-590, KURARAY POLYOL C-2050, KURARAY POLYOL C-2090 and KURARAY POLYOL C-3090 is from Kuraray u s company (Kuraray America, Inc.) obtain those.
Except polycarbonate polyol, can also add other polyhydric alcohol, such as polyoxyalkylene polyol.These polyoxygenated Alkene polyhydric alcohol includes such as water, ethylene glycol, diethylene glycol, Propylene Glycol, dipropylene glycol, glycerol, 1,2,6- hexanetriol, 1,1,1- tri- The alkylene oxide adduct of hydroxymethyl ethane or propane, tetramethylolmethane etc..Alkylene oxide for preparing polyoxyalkylene polyol is usual With 2 to 4 carbon atoms.Oxirane, expoxy propane and their mixture are specially suitable.Can also use aromatics many The alkylene oxide adduct of first alcohol, such as bisphenol-A.Acrylic polyol can be also used, the copolymerization of such as acrylic monomer adds Compound, the acrylic monomer such as ethyl acrylate, butyl acrylate, acrylic acid, methyl methacrylate or have hydroxylation The styrene acrylic acid 2- hydroxyl ethyl ester of acrylic monomer or acrylic acid 4- hydroxy butyl ester etc., as long as acrylic polyol is not It is unsaturated polyol.The polyhydric alcohol based on natural product can also be used, for example, by Oleum Ricini etc. be derived polynary Alcohol.
Reactant mixture can also include silane coupler.Silane coupler is well-known bifunctionality silane chemical combination Thing, the compound has silane group at one end, has reactive group in the other end.The example of reactive functional groups includes sulfur Alcohol groups, amino group, oh group, epoxide group and isocyanate groups.Specially suitable silane coupler be with ammonia Base or the silane coupler of isocyanate functional group.So, reaction is final to be incorporated to jointly with reactant mixture for silane coupler Polymer in.The example of commercially available silane coupler includes can be from the win of Kansas State Europe Forlan Parker wound industry Amino-functional silane DYNASYLAN 1122 that (Evonik Industries) is obtained and can be from Ohio Si Telang Weir The isocyanide that obtains of MomentivePerformanceMaterials (Momentive Performance Materials, Strongsville, OH) Acid esters functional silane SILQUEST A-LINK 25.
Reactant mixture can also include curing catalysts.If you are using, curing catalysts can be typically used for shape Any one in the curing catalysts of generating polyurethane polymer.Typical catalysts for polyurethanes is for aminated compoundss (particularly Tertiary amine, such as triethylenediamine (TEDA, Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane or DABCO), dimethyl cyclohexyl amine (DMCHA) and dimethylethanolamine (DMEA)) and metal complex.Lead, stannum, the metal complex of bismuth and zinc are typically used as gathering The catalyst of urethane polyreaction.Specifically, bismuth carboxylate and zinc polycarboxylate and alkyl tin carboxylate are usually used.In this public affairs In opening, suitably tin catalyst, such as FASCAT 4202 (dibutyl tin laurate) in general, which can be from guest's sunset method The Arkema (Arkema, Inc.King of Prussia, PA) in Ni Ya state Pu Lushiwang city is commercially available.
If desired, reactant mixture optionally includes various other additives.Wherein, suitably add Agent is dyestuff, pigment, UV stabilizer, antioxidant, UV absorbent, modifying agent, performance synergist or combinations thereof.Such add Plus agent can provide feature such as color and UV stability, and stability and the anti-flammability of formed product can be improved.
In some embodiments, at least one dyestuff or pigment are added in reactant mixture so that formed is poly- Urethane pearl tack coat is coloured pearl tack coat.Coloured pearl tack coat generally comprises coloring agent, and coloring agent is pigment, dye in general Material or combinations thereof.It is typically used as the more difficult colour fading of pigment ratio dyestuff of pigment, it is intended that pigment is under various conditions often Its color and longer than the dyestuff retention time can be kept.In general, if there is additive, then pearl tack coat includes about 70 The polyurethane of weight % to about 99 weight %, remaining material is coloring agent or other optional additives of effective dose.
As described above, reactant mixture is applied to microsphere layer and carries out being cured to form polyurethane pearl tack coat. The solidification can be subject to following impact：Apply heat, make reactant mixture stand a period of time or combinations thereof at room temperature.Logical Often, heating be in order to accelerate solidification.About 50 DEG C to about 120 DEG C of temperature can be used.Can by for example being carried out using baking oven plus Heat.
The thickness of the polyurethane pearl tack coat for being formed is typically about 50 microns to 250 microns (2 mils are to 10 mils), its In generally specially suitable thickness be for about 75 microns to 200 microns (3 mils are to 8 mils).It should be appreciated that thickness can be used at this Pearl tack coat outside a little scopes；However, if pearl tack coat is too thin, which may provide enough supports for microsphere, So that they become loosening.
In some embodiments, the method may also include and apply supporting layer to polyurethane pearl tack coat.In solidification Before supporting layer can be made to contact with polyurethane pearl tack coat, that is to say, that supporting layer can be made to contact with reactant mixture layer so that when During reaction mixture cured, pearl tack coat adheres to supporting layer.Supporting layer can be single or multiple lift product.Suitable supporting layer Example include film layer, tissue layer or non-woven layer.
In other embodiments, supporting layer is made to contact with polyurethane pearl tack coat after solidification.Suitable supporting layer Example include adhesive phase, film layer, tissue layer or non-woven layer.The example of suitably binding agent include contact adhesive, Heat-activatable adhesive and laminating adhesive.Adhesive phase can be as needed by backing member covering be peeled off, with using front protection bonding Agent surface is from pollution.Adhesive phase can be used alone as supporting layer, or adhesive phase can be used for polyurethane pearl tack coat Adhere to various substrates, such as film, fabric and non-woven fabric.In addition, various substrates such as film, fabric and non-woven fabric can be led to Cross that mechanical system is such as sutured or hot laminating adheres to polyurethane pearl tack coat.Especially desirable substrate is fabric so that institute's shape The product for becoming is clothes product.
The product being consequently formed is sometimes referred to as " intermediate ".So-called intermediate, which means wherein polymer support The product that layer is attached with product.Intermediate itself is not retroreflective articles, but becomes back after removing polymer carrier layer Penetrate product.
The intermediate can be made to experience additional step immediately generating final retroreflective articles, or can store intermediate with For rear, transport to another location or experience additional treatment step, cut, be attached to substrate etc..It is generally desirable to form this Intermediate, is not exposed optical element because of storing to the intermediate, transported or be processed.Once expose optics unit Part, even if intermediate includes polyurethane pearl tack coat, they such as are also worn, dye at the potential damage.When needed, remove Polymer carrier layer is to form final retroreflective articles.
Said method can be used to prepare multiple retroreflective articles.Disclosed herein is the retroreflective articles of the layer including optical element. Optical element is Transparent microspheres and at least one reflecting layer.Optical element is embedded in polyurethane pearl tack coat, wherein poly- ammonia Product of the ester pearl tack coat comprising reactant mixture, the reactant mixture is polynary comprising at least one fatty poly-ester carbonate Alcohol and at least one polyisocyanates, and wherein reactant mixture does not contain the polyhydric alcohol containing unsaturated group.Retouch in detail above The reactant mixture for suitably forming polyurethane pearl tack coat is stated.Reflecting layer can be reflective metal layer, electrolyte reflecting layer or Combinations thereof.Retroreflective articles have washability.
So-called washability, which means that the retroreflective articles of the disclosure can be washed without forfeiture product desirable characteristics, i.e., Retroreflective.The washability of retroreflective articles can be described in a variety of ways.The example of good scourability is in United States Patent (USP) It is described in open No.2011/0292508 (Huang et al.), is such as maintained at 5/0.2 angle extremely after 15 washings Few about 100 candelas/lux/rice2.In some embodiments, retroreflective articles are positively retained at 5/0.2 after 15 washings At least about 200 candelas at angle/lux/rice2.In other embodiments, retroreflective articles can after 15 washings At least about 300 candelas/lux/rice being maintained at 5/0.2 angle2.
In some embodiments, it is desirable that, the surface of retroreflective articles is discrete.So-called discontinuous, which means Region on the surface is without microsphere and pearl tack coat, and wherein discontinuous part is surrounded by continuum.These discontinuous portions It can be favourable to separate in multiple reasons.In some embodiments, discontinuous part can form pattern or design.The pattern or Design can be the forms such as labelling, logo.In other embodiments, discontinuous part can random arrangement or with discontinuous pattern Arrangement.In addition to the visual effect of discontinuous part, discontinuous part can provide enhanced breathability for retroreflective articles.So-called Gas means that gas and/or dampness can more easily pass through retroreflective articles.The effect of enhanced breathability is：This based article It is put on more comfortable.This is especially desirable for builder, fireman, emergency worker and players.With discontinuous section The example of various designs of retroreflective articles be found in Fig. 25 of United States Patent (USP) No.8,256,025.
Retroreflective articles with discontinuous surface can be prepared in a number of different ways.Specially suitable mode includes：From Optical element and pearl tack coat are partly removed in the part on the surface.This removes and can pass through cutting, scraping, punching and other conjunctions Suitable mechanical system is realized.
Retroreflective articles can be independent product, or layer of polyurethane can have be attached with which so that retroreflective articles become more The supporting layer of a part for big product.Supporting layer may include adhesive phase, film layer, tissue layer or non-woven layer.Suitably prop up The example of support layer is as described above.
The example of disclosure product is provided in the accompanying drawings.Fig. 1 is the sectional view of the embodiment of the intermediate of the disclosure. In FIG, intermediate includes polyurethane pearl tack coat 10, Transparent microspheres 20, reflecting layer 30 and carrier layer 40.Carrier layer 40 Including sheet layer 44 and thermoplastic polymer carrier's material coating 42.
Fig. 2 shows the alternative embodiment of the intermediate of the disclosure.In fig. 2, intermediate includes polyurethane pearl Tack coat 10, Transparent microspheres 20, reflecting layer 30 and carrier layer 40.Carrier layer 40 includes that sheet layer 44 and thermoplastic polymer are carried Body material coating 42.Fig. 2 also includes supporting layer 50.
The embodiment that Fig. 3 is shown in which Fig. 1 of removed carrier layer 40.In figure 3, the product includes polyurethane Pearl tack coat 10, Transparent microspheres 20 and reflecting layer 30.
The embodiment that Fig. 4 is shown in which Fig. 2 of removed carrier layer 40.In the diagram, the product includes polyurethane Pearl tack coat 10, Transparent microspheres 20, reflecting layer 30 and supporting layer 50.
The clothes product being also disclosed containing retroeflection applique.These clothes products are included with the first first type surface and The fabric of two first type surfaces；And the retroeflection applique with the first first type surface attachment of the fabric.The retroeflection applique is above-mentioned retroeflection Product.Various fabrics are all suitable.Clothes product, as described above, be also washability.
By multiple attachment technology, such as mechanical attachment or binding agent attachment, retroeflection applique can be attached to fabric face. The example of mechanical attachment technology includes, for example, sutures and hot laminating.In binding agent attachment, binding agent can be applied to glue to pearl Knot layer, or backing layer can be applied to pearl tack coat and apply adhesive phase to backing layer.
The example of proper adhesive layer includes contact adhesive, heat-activatable adhesive and laminating adhesive.Can be by coating Or by adhesive phase to be applied to pearl tack coat or the back of the body adhesive phase for being formed with pearl tack coat or backing layer lamination Lining.
Multiple contact adhesives are suitable, including viscosifying natural rubber, synthetic rubber, tackified styrene block copolymerization Thing, polyvinylether, poly- (methyl) acrylate, polyurethane, polyureas, poly alpha olefin and organosilicon.Contact adhesive can be with stripping Backing member is covered, to protect binding agent before substrate is adhered to.
Heat-activatable adhesive is very similar with contact adhesive but needs to apply heat to become tacky.Heat-activatable adhesive An advantage be, as which is not tacky at room temperature, therefore its be not usually required to peel off backing member protected before substrate is adhered to Shield adhesive phase.
Generally, if using laminating adhesive, adhesive phase is bonded to substrate immediately to form adhesive group bottom bonding. The example of laminating adhesive includes hot-melt adhesive, adhesive dispersion and suspension and solidification binding agent such as cyano group Acrylate.
Multiple clothes products are suitable to be attached retroeflection applique.The example of such clothes product includes, for example, vest, such as road The safety vest that workman often dresses is built on road, but also includes other kinds of laundry multiple.Example includes shirt, sweater, folder Gram, overcoat, trousers, medicated underpants, socks, shoes, glove, belt, medicated cap, western-style clothes, integral trousers etc..
Fig. 5 shows the clothes product of the disclosure.Vest in Fig. 5 includes retroeflection applique 100.Retroeflection applique 100 is permissible It is, for example, the product of Fig. 1.
The disclosure includes embodiments below：
In these embodiments be retroreflective articles.First embodiment includes retroreflective articles, and the retroreflective articles include： Polyurethane pearl tack coat；With the layer of the optical element being partially embedded in the pearl tack coat, the optical element includes：Transparent beads Body and at least one reflecting layer；Wherein the polyurethane pearl tack coat includes the product of reactant mixture, the reactant mixture Comprising at least one aliphatic polycarbonate polybasic alcohol and at least one polyisocyanates, and wherein reactant mixture contains The polyhydric alcohol of unsaturated group.
Embodiment 2 is the retroreflective articles of embodiment 1, and wherein reactant mixture is also comprising at least one other polynary Alcohol.
Embodiment 3 is the retroreflective articles of embodiment 1 or embodiment 2, and wherein reactant mixture also includes at least two Plant other polyhydric alcohol.
Embodiment 4 is the retroreflective articles of embodiment 3, and at least one in the other polyhydric alcohol of two of which includes official Polyhydric alcohol of the energy degree more than 2, and at least one in the other polyhydric alcohol of two of which is not PEPA.
Embodiment 5 is retroreflective articles of the embodiment 1 to any one of embodiment 4, many isocyanides of wherein at least one Acid esters includes aliphatic polyisocyante.
Embodiment 6 is retroreflective articles of the embodiment 1 to any one of embodiment 4, many isocyanides of wherein at least one Acid esters includes aromatic polyisocyanate.
Embodiment 7 is retroreflective articles of the embodiment 1 to any one of embodiment 6, wherein with respect to polyhydric alcohol Amount, the amount of the polyisocyanates being present in reactant mixture includes the polyisocyanates of stoichiometric excess.
Embodiment 8 is retroreflective articles of the embodiment 1 to any one of embodiment 7, and wherein reactant mixture is also wrapped Containing at least one silane coupler.
Embodiment 9 is the retroreflective articles of embodiment 8, and wherein silane coupler includes that isocyanate-functional is silane coupled Agent.
Embodiment 10 is the retroreflective articles of embodiment 8, and wherein silane coupler includes amino-functional silane coupler.
Embodiment 11 be retroreflective articles of the embodiment 1 to any one of embodiment 10, wherein reactant mixture also Comprising at least one curing catalysts.
Embodiment 12 is retroreflective articles of the embodiment 1 to any one of embodiment 11, and the wherein product is washable Property.
Embodiment 13 is retroreflective articles of the embodiment 1 to any one of embodiment 12, also includes and polyurethane pearl The supporting layer of tack coat attachment, the supporting layer includes adhesive phase, film layer, tissue layer or non-woven layer.
The invention also discloses clothes product.Embodiment 14 includes clothes product, and the clothes product includes：With first First type surface and the fabric of the second first type surface；And the retroeflection applique being attached with the first first type surface of the fabric, the retroeflection applique includes： Polyurethane pearl tack coat；The layer of the optical element being partially embedded in pearl tack coat, the optical element includes：Transparent microspheres and At least one reflecting layer；Wherein polyurethane pearl tack coat is many comprising at least one aliphatic polycarbonate polybasic alcohol and at least one The product of isocyanates, the wherein reactant mixture do not contain the polyhydric alcohol containing unsaturated group；And bond with polyurethane pearl The supporting layer of layer attachment, the supporting layer includes adhesive phase, film layer, tissue layer or non-woven layer, wherein the supporting layer attachment The first first type surface to fabric.
Embodiment 15 is the clothes product of embodiment 14, wherein supporting layer by mechanical attachment or adhesives with The first first type surface attachment of fabric.
Embodiment 16 is the clothes product of embodiment 14 or embodiment 15, and the wherein clothes product is washability 's.
Invention also discloses the method for preparing product.Embodiment 17 includes a kind of method for preparing product, the method Including：The polymer carrier layer with the first first type surface and the second first type surface is provided；Transparent microspheres are provided；By Transparent microspheres It is partially embedded in the first first type surface of polymer carrier layer so that pearl is at least in part from the first master meter of polymer carrier layer Face projects, to form microsphere layer；Deposit at least a portion of the first first type surface of polymer carrier layer and microsphere layer One or more reflecting layer；There is provided comprising the anti-of at least one aliphatic polycarbonate polybasic alcohol and at least one polyisocyanates Mixture is answered, and wherein the reactant mixture does not contain the polyhydric alcohol containing unsaturated group；Reactant mixture is applied to microsphere Body layer；And reaction mixture cured is made to form polyurethane pearl tack coat.
Embodiment 18 is the method for embodiment 17, and wherein reactant mixture is also comprising at least one other polynary Alcohol.
Embodiment 19 is the method for embodiment 17, and wherein reactant mixture is also other polynary comprising at least two Alcohol.
Embodiment 20 is the method for embodiment 19, and at least one in the other polyhydric alcohol of two of which includes sense Polyhydric alcohol of the degree more than 2, and at least one in the other polyhydric alcohol of two of which is not PEPA.
Embodiment 21 is method of the embodiment 17 to any one of embodiment 20, wherein at least one polyisocyanic acid Ester includes aliphatic polyisocyante.
Embodiment 22 is method of the embodiment 17 to any one of embodiment 20, wherein at least one polyisocyanic acid Ester includes aromatic polyisocyanate.
Embodiment 23 is method of the embodiment 17 to any one of embodiment 22, wherein with respect to polyhydric alcohol Amount, the amount of the polyisocyanates being present in reactant mixture includes the polyisocyanates of stoichiometric excess.
Embodiment 24 is method of the embodiment 17 to any one of embodiment 23, and wherein reactant mixture also includes At least one silane coupler.
Embodiment 25 is the method for embodiment 24, and wherein silane coupler includes that isocyanate-functional is silane coupled Agent.
Embodiment 26 is the method for embodiment 24, and wherein silane coupler includes amino-functional silane coupler.
Embodiment 27 is method of the embodiment 17 to any one of embodiment 26, and wherein reactant mixture also includes At least one curing catalysts.
Embodiment 28 is method of the embodiment 17 to any one of embodiment 27, wherein makes reaction mixture cured Include reacting by heating mixture to form polyurethane pearl tack coat, make reactant mixture place more than 2 weeks, or they at room temperature Combination.
Embodiment 29 is method of the embodiment 17 to any one of embodiment 28, also includes to be attached to supporting layer Polyurethane pearl tack coat, the wherein supporting layer include adhesive phase, film layer, tissue layer or non-woven layer.
Embodiment 30 is the method for embodiment 29, and wherein supporting layer being attached to polyurethane pearl tack coat includes, Reaction mixture cured is made before forming polyurethane pearl tack coat, to make supporting layer contact with polyurethane pearl tack coat.
Embodiment 31 is the method for embodiment 29, and wherein supporting layer being attached to polyurethane pearl tack coat includes, After reaction mixture cured being made to form polyurethane pearl tack coat, by supporting layer adhesives to polyurethane pearl tack coat.
Embodiment 32 is method of the embodiment 17 to any one of embodiment 31, also includes removing polymer carrier Layer is to generate retroreflective articles.
Embodiment 33 is the method for embodiment 32, also includes, before removing polymer carrier layer, product is adhered to To substrate.
Embodiment 34 is the method for embodiment 33, and wherein, substrate includes clothes product.
Embodiment
These embodiments are only used for exemplary purpose, and have no intention to limit the scope of the appended claims.Remove Non- otherwise indicated, all numbers otherwise in the remaining part of embodiment and description, percent, ratio etc. are all by weight Meter.Except as otherwise noted, solvent otherwise used and other reagents all derive from the Sigma of Milwaukee, WI, USA Aldrich Chemical company (Sigma-Aldrich Chemical Company；Milwaukee,Wisconsin).Using following Abbreviation：Rpm=revolutions per minute；The sec=second；Cm=centimetre；Mm=millimeter；Min=minute；G=gram；M=rice.Term " weight % ", " % weight " and " wt% " is used interchangeably.Retroreflective with standard unit cd/ (lx.m2) list, that is to say, that Candela/lux/rice2.
Abbreviations table
Synthetic example S1：Glass bead layer through steam coating：
Temporary glass bead carrier is prepared according to the flow process as described in United States Patent (USP) No.5,474,827.Polyethylene layer is coated with On paper backings.Polyethylene layer is heated, and the bead by diameter in 40 microns to 90 micrometer ranges rushes down and sinks to In polyethylene.Submergence depth is less than the diameter of bead, and a part of microsphere keeps being exposed on the surface of polyethylene.With Aluminum metal thin layer carries out steam coating to coated glass bead layer, to form aluminum metal mirror layer.
Embodiment 14 and comparative example C1：
Pearl bonding coat is applied to the sample of the glass bead layer material through steam coating described in synthetic example S1.Real Apply the pearl that example 14 employed based on Merlon to bond, for comparative example C1, employ the pearl based on polycaprolactone and bond.
Prepare pearl bonding reactive mixture：
According to listed order, component shown in table 1 is added in Max 60SpeedMixer cup, closes the lid, and use FlackTec company (FlackTec Inc) SpeedMixer DAC 150FVZ is by mixture with 1600rpm centrifugal mixer 20 seconds. With notch bar coater by gained mixture be coated on through steam coating glass bead layer material 12 × 24 inches (30.5 × 61.0cm) on sheet material, moistening thickness is 0.15mm (6 mil).By coated sheet material heating 4 in 150 (66 DEG C) baking oven Minute.Take out coated sheet material from baking oven, and with hand-held cylinder by a piece of 14 × 26 inches (35.6 × 66.0cm) Polyester textile lamination in coating.Then in the baking oven of 215 (102 DEG C), the laminates are heated 15 minutes.From baking oven Middle taking-up laminates, and make which stand 2 weeks at room temperature, in this period, carrier is peelled off, so as to expose glass microspheres list The aforementioned embedded surface of layer is to prepare retroreflective fabric product.
Table 1
Reagent Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparative example C1
Silane -1 (g) 1.09 1.09 0.79 1.04 1.05
ISO-1(g) 5.34 5.34 4.03 5.11 5.34
PC glycol -1 (g) 19.69 0 0 0 0
PC glycol -2 (g) 0 19.69 0 18.89 0
PC glycol -3 (g) 0 0 22.23 0 0
PC glycol -4 (g) 0 0 0 2.87 0
PE glycol (g) 0 0 0 0 19.69
BPA glycol (g) 2.99 2.99 2.25 0 2.99
Triol -1 (g) 0.93 0.93 0.70 0 0.93
Triol -2 (g) 0 0 0 1.63 0
Curing catalysts -1 (g) 0.036 0.036 0.036 0 0.072
Curing catalysts -2 (g) 0 0 0 0.47 0
Washability is tested：
The test sample of the textile article in embodiment 14 and comparative example C1 passes through 2 × 10 inches (5.1 × 25.4cm) Textile article applique be sewn onto a piece of 30 × 25 inches (76.2 × 63.5cm) weight for 270g/m2Polyester/cotton 85/15 glimmering On light orange fabric.By second identical fabric to be attached to the opposition side of test sample around edge sewn seams, to be formed The double-layer structural that test applique is faced outwardly.By the test sample in embodiment 14 and comparative example C1 in 21 DEG C (70) and 50% 3 weeks or 8 months aging is carried out under RH, and and then with UniMac UF50 washer-extractor according to method ISO15797 (“Textiles-Industrial washing and finishing procedures for testing of Workwear " (industrialization of textile working clothing washing press testing process with whole)) in method 8 washed.Use Leonard The whole machine of pressing of the IM-48 pipe tunnel formula of Automation Co., Ltd (Leonard Automatics, Inc.) dries these samples according to method of testing Product.As a result illustrate in table 2 and table 3.Even if embodiment 14 is shown after 8 months aging periods, higher after being washed Retroreflective conservation rate.
Table 2：Washing data after 3 weeks aging periods
Table 3：Washing data after 8 months aging periods

Claims (21)

1. a kind of retroreflective articles, including：
Polyurethane pearl tack coat；With
Optical element layer, is embedded in the pearl tack coat optical element portion, and the optical element includes：
Transparent microspheres, and at least one reflecting layer；
Wherein the polyurethane pearl tack coat includes the product of reactant mixture, and the reactant mixture is comprising at least one Aliphatic polycarbonate polybasic alcohol and at least one polyisocyanates, and wherein the reactant mixture is not contained containing unsaturated group The polyhydric alcohol of group.
2. retroreflective articles according to claim 1, the wherein reactant mixture are also comprising at least one other polynary Alcohol.
3. retroreflective articles according to claim 1, the wherein reactant mixture are also other polynary comprising at least two Alcohol.
4. retroreflective articles according to claim 3, the wherein at least one in described two other polyhydric alcohol includes official Polyhydric alcohol of the energy degree more than 2, and at least one wherein in described two other polyhydric alcohol is not PEPA.
5. retroreflective articles according to claim 1, wherein at least one polyisocyanates include many isocyanides of aliphatic Acid esters.
6. retroreflective articles according to claim 1, wherein at least one polyisocyanates include aromatics polyisocyanic acid Ester.
7. retroreflective articles according to claim 1, wherein with respect to the amount of polyhydric alcohol, are present in the reactant mixture The amount of the polyisocyanates include the polyisocyanates of stoichiometric excess.
8. retroreflective articles according to claim 1, the wherein reactant mixture are also comprising at least one silane coupler.
9. retroreflective articles according to claim 1, the wherein reactant mixture are also comprising at least one curing catalysts.
10. retroreflective articles according to claim 1, the wherein product is washability.
11. retroreflective articles according to claim 1, also include the supporting layer with polyurethane pearl tack coat attachment, institute Stating supporting layer includes adhesive phase, film layer, tissue layer or non-woven layer.
A kind of 12. clothes products, including：
Fabric, the fabric has the first first type surface and the second first type surface；With
Retroeflection applique, the retroeflection applique is attached to first first type surface of the fabric, and the retroeflection applique includes：
Polyurethane pearl tack coat；
Optical element layer, is embedded in the pearl tack coat optical element portion, and the optical element includes：
Transparent microspheres, and at least one reflecting layer；
Wherein the polyurethane pearl tack coat is comprising at least one aliphatic polycarbonate polybasic alcohol and at least one polyisocyanic acid The product of ester,
Wherein the reactant mixture does not contain the polyhydric alcohol containing unsaturated group；
With
Supporting layer, the supporting layer is attached to the polyurethane pearl tack coat, and the supporting layer includes adhesive phase, film layer, knits Nitride layer or non-woven layer, the wherein supporting layer are attached to first first type surface of the fabric.
A kind of 13. methods for preparing product, methods described includes：
The polymer carrier layer with the first first type surface and the second first type surface is provided；
Transparent microspheres are provided；
The Transparent microspheres are partially embedded in first first type surface of the polymer carrier layer so that the pearl is extremely Partially project from first first type surface of the polymer carrier layer, to form microsphere layer；
In at least a portion of first first type surface of the polymer carrier layer and the microsphere layer deposit one or Multiple reflecting layer；
Reactant mixture comprising at least one aliphatic polycarbonate polybasic alcohol and at least one polyisocyanates is provided, and Wherein the reactant mixture does not contain the polyhydric alcohol containing unsaturated group；
The reactant mixture is applied to the microsphere layer；And
The reaction mixture cured is made to form polyurethane pearl tack coat.
14. methods according to claim 13, wherein with respect to the amount of polyhydric alcohol, are present in the reactant mixture The amount of the polyisocyanates includes the polyisocyanates of stoichiometric excess.
15. methods according to claim 13, the wherein reactant mixture are also comprising at least one silane coupler.
16. methods according to claim 13, the wherein reactant mixture are also comprising at least one curing catalysts.
17. methods according to claim 13, also include for supporting layer to be attached to the polyurethane pearl tack coat, wherein institute Stating supporting layer includes adhesive phase, film layer, tissue layer or non-woven layer.
18. methods according to claim 17, wherein the supporting layer being attached to the polyurethane pearl tack coat includes The reaction mixture cured is made the supporting layer is made before forming the polyurethane pearl tack coat with the polyurethane pearl Tack coat is contacted.
19. methods according to claim 17, wherein the supporting layer being attached to the polyurethane pearl tack coat includes Making the reaction mixture cured to be formed after the polyurethane pearl tack coat by the supporting layer adhesives to institute State polyurethane pearl tack coat.
20. methods according to claim 13, also include to remove the polymer carrier layer to generate retroreflective articles.
21. methods according to claim 20, are additionally included in before removing the polymer carrier layer and glue the product It is attached to substrate.
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US20170146704A1 (en) 2017-05-25

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